US3807999A - Photo-cycloaddition polymerization of bis-anthracenes - Google Patents

Photo-cycloaddition polymerization of bis-anthracenes Download PDF

Info

Publication number
US3807999A
US3807999A US00233325A US23332572A US3807999A US 3807999 A US3807999 A US 3807999A US 00233325 A US00233325 A US 00233325A US 23332572 A US23332572 A US 23332572A US 3807999 A US3807999 A US 3807999A
Authority
US
United States
Prior art keywords
bis
anthracene
photo
polymers
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US00233325A
Other languages
English (en)
Inventor
Schrijver F De
G Delzenne
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert NV
Original Assignee
Agfa Gevaert NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Agfa Gevaert NV filed Critical Agfa Gevaert NV
Priority to US440503A priority Critical patent/US3892642A/en
Application granted granted Critical
Publication of US3807999A publication Critical patent/US3807999A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
    • G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/28—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using thermochromic compounds or layers containing liquid crystals, microcapsules, bleachable dyes or heat- decomposable compounds, e.g. gas- liberating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable

Definitions

  • the polymers formed can be degraded by exposing to a heat treatment, or by irradiation at 254 nm.
  • the degraded polymers can be repolymerized upon ultraviolet irradiation at about 365 nm in the absence of oxygen.
  • a method of recording information is described, by using the photo-cycloaddition polymerization with ultraviolet light, and the degradation by exposing to heat or to radiation at 254 nm.
  • the invention relates to the photo-cycloaddition polymerization of bis-anthracenes.
  • anthracene and its derivatives substituted at the 9-position can be dimerized in the presence of light.
  • Bis-anthracenes also have been prepared but they were studied to determine the nature of intramolecular reactions between the two anthracene groups present in the same molecule.
  • a process for the photo-cycloaddition polymerization of hisanthracenes comprises exposing to ultraviolet radiation, in the absence of oxygen, bisanthracenes corresponding to one of the general formulae:
  • R represents an alkylene group of two to 10 carbon atoms and n is l or 2.
  • the irradiation of the bisanthracenes with ultraviolet radiation occurs in solution in halogenated alkanes such as dichloromethane, after removal of all oxygen from the solution by bubbling an inert gas, such as dry oxygen-free argon therethrough.
  • the bis-anthracenes may also be irradiated in the solid state, preferably in the form of a thin coating applied from solution to any support, such as paper, naturally also in the absence of oxygen.
  • the irradiation with ultraviolet radiation should be performed in the absence of oxygen, since oxygen acts as an inhibitor for the photo-cycloaddition polymerization reaction. it has been observed that this polymerization reaction is reversible. Indeed, when the polymers are exposed to a heat treatment, they are degraded, which results in the formation of anthracene end groups. The same effect can be obtained by irradiation at 254 nm.
  • the degraded polymers can be repolymerized by exposing them again to ultraviolet radiation at about 365 nm in the absence of oxygen.
  • polymers are soluble in haloalkanes such as dichloromethane and chloroform. In some cases they become insoluble in these solvents as a result of crystallization. In these cases the polymers were found to be soluble in dimethylsulphoxide, thus proving that no cross-linked structures were formed.
  • the photo-cycloaddition polymers can be formed from solutions into transparent films, which are more brittle when the number of CH groups forming the alkylene group between two anthracene ester groups is small.
  • the polymer chains can be reformed on exposure with ultraviolet radiation of 365 nm or higher intensities, naturally in the absence of oxygen.
  • ultraviolet radiation 365 nm or higher intensities
  • the occurrence of excimer fluorescence can be used as a very interesting photographic procedure.
  • this layer can be image-wise exposed to heat, eg by means of an infrared laser, so that the bonds between two anthracene groups are destroyed in the exposed places.
  • the image thus formed into the layer can be scanned with an ultraviolet laser and recorded with a photocell sensitive to the excimer-fluorescence occurring in those places where the polymer has been destroyed by the infrared laser.
  • 9-anthraldehyde is made to react in a methanol medium with sodium borohydride, and the 9-hydroxyalkylanthracene formed is converted with a diacid chloride such as succinoyl chloride, adipoyl chloride pimeloyl chloride, suberoyl chloride azeloyl chloride and sebacoyl chloride.
  • a diacid chloride such as succinoyl chloride, adipoyl chloride pimeloyl chloride, suberoyl chloride azeloyl chloride and sebacoyl chloride.
  • PREPARATION 8 Hexamethylene Diester of 9-Anthroic Acid 2.4 g 9-anthroyl chloride were dissolved in 100 m1 of benzene and heated for 6 hours at 78C with 0.59 g of 1,6-hexanediol and 0.79 g of pyridine. The solid matter was isolated and the solvent was evaporated in vacuo. The product was purified as described in preparation 7, but from a chloroform solution.
  • Example Di-ester from Concentration Irradiation Molecular Melting preparation during irratime in weight range no. diation in hours in C moles/litre The molecular weight was determined in a laboratory vapour pressure osmometer in chloroform solution. The melting range was determined in a differential scanning colorimeter under nitrogen atmosphere with a heating ratio of 8C/minute.
  • the photo-cycloaddition polymers were characterized by elemental analysis, infrared spectrometry, molecular weights and thermal properties.
  • the polymers were found to decompose above their melting range. Since the polymers are decomposed to monomers by heating and can be repolymerized when exposed to ultraviolet radiation, the possibility exists of repeatedly polymerizing the monomer with ultraviolet radiation in the absence of oxygen and of depolymerizing thermally.
  • the polymers form transparent films when applied from solution to a support, which films are more brittle when the number of carbon atoms between the anthrylmethyl ester groups is small.
  • EXAMPLE 6 Decamethylene diester of 9-anthroic acid of preparation 7 was dissolved in dichloromethane in tubes of beton-silicate glass to a concentration of 0.2 mole/litre. The solution was freed from oxygen by bubbling argon through it for 30 minutes. Photopolymerization occurred by exposure for 48 hours to light having a maximum of intensity at 366 nm. It formed was separated by adding an excess of acetone whereafter the polymer was filtered and dried in vacuo at 40C. The polymer had an intrinsic viscosity of 0.65 which corresponds with a molecular weight of 21,000.
  • EXAMPLE 7 The process of Example 6 was repeated with hexamethylene diester of 9-anthroic acid. The polymer formed upon exposure to ultraviolet radiation was insoluble in dichloromethane and precipitated.
  • EXAMPLE 8 250 mg of poly(decamethylene diester of 9-anthroic acid) according to Example 6 were dissolved in 10 ml of chloroform and the solution formed was applied to a polyethylene terephthalate support. The thickness of the layer before drying was approximatively 0.125 mm. The layer could also be applied to a glass support or a quartz plate.
  • the layer was heated for 60 seconds at -l60C.
  • fluorescent radiation having a maximum at 448 nm was observed.
  • the intensity of the fluorescence increased with the time of heating.
  • the layer was heated image-wise, e.g. with a CO -laser, a corresponding fluorescent image was formed.
  • the same effect could be obtained when, instead of heating, the polymer layer was exposed to radiation of 254 nm.
  • This exposure could also be performed imagewise by irradiating the layer through a transparent original with a low-pressure mercury vapour lamp, or by scanning the image with a Nd-laser or a HeCdlaser.
  • Method of recording information comprising information-wise exposing to heat or ultraviolet radiation of 254 nm a recording material comprising a support and a layer of photo-cycloaddition polymer of bisanthracene, whereby said photo-cycloaddition polymer layer is information-wise degraded and a fluorescence pattern corresponding to said information-wise exposure is obtained, said photo-cycloaddition polymer of bisanthracene being obtained by exposing to ultraviolet radiation, in the absence of oxygen, bis-anthracene corresponding to one of the formulae:
  • R represents an alkylene group of from two to 10 carbon atoms and n is l or 2.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
US00233325A 1972-03-07 1972-03-09 Photo-cycloaddition polymerization of bis-anthracenes Expired - Lifetime US3807999A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US440503A US3892642A (en) 1972-03-07 1974-02-07 Photo-cycloaddition polymerization of bis-anthracene

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB737671A GB1358274A (en) 1972-03-07 1972-03-07 Photocycloaddition polymerization of bisanthracenes

Publications (1)

Publication Number Publication Date
US3807999A true US3807999A (en) 1974-04-30

Family

ID=9831959

Family Applications (1)

Application Number Title Priority Date Filing Date
US00233325A Expired - Lifetime US3807999A (en) 1972-03-07 1972-03-09 Photo-cycloaddition polymerization of bis-anthracenes

Country Status (5)

Country Link
US (1) US3807999A (cg-RX-API-DMAC10.html)
BE (1) BE780294A (cg-RX-API-DMAC10.html)
DE (1) DE2212427A1 (cg-RX-API-DMAC10.html)
FR (1) FR2130443B1 (cg-RX-API-DMAC10.html)
GB (1) GB1358274A (cg-RX-API-DMAC10.html)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3892642A (en) * 1972-03-07 1975-07-01 Agfa Gevaert Nv Photo-cycloaddition polymerization of bis-anthracene
US4182665A (en) * 1974-04-01 1980-01-08 Japan Storage Battery Co., Ltd. Method for curing photo-curable composition
US4413052A (en) * 1981-02-04 1983-11-01 Ciba-Geigy Corporation Photopolymerization process employing compounds containing acryloyl group and anthryl group
US5512329A (en) * 1982-09-29 1996-04-30 Bsi Corporation Substrate surface preparation
WO2001097217A3 (en) * 2000-06-16 2002-05-02 Optilink Ab Optical storage using materials comprising chromophore oligomers which can undergo cycloaddition
WO2003088234A1 (en) * 2002-04-11 2003-10-23 Inphase Technologies, Inc. Holographic storage media
US20050026068A1 (en) * 2001-11-01 2005-02-03 Evangelos Gogolides Polycarbocyclic derivatives for modification of resist, optical and etch resistance properties
WO2019002273A1 (en) * 2017-06-26 2019-01-03 Solvay Specialty Polymers Usa, Llc AROMATIC POLYMERS THAT CAN BE OBTAINED BY CYCLOADDITION REACTION

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2980535A (en) * 1954-01-05 1961-04-18 Feldmuhle Papier Und Zellstoff Light sensitive layers of synthetic materials
US3622321A (en) * 1968-12-24 1971-11-23 Agfa Gevaert Nv Photodimerization and photopolymerization of bis-maleimides

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2980535A (en) * 1954-01-05 1961-04-18 Feldmuhle Papier Und Zellstoff Light sensitive layers of synthetic materials
US3622321A (en) * 1968-12-24 1971-11-23 Agfa Gevaert Nv Photodimerization and photopolymerization of bis-maleimides

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3892642A (en) * 1972-03-07 1975-07-01 Agfa Gevaert Nv Photo-cycloaddition polymerization of bis-anthracene
US4182665A (en) * 1974-04-01 1980-01-08 Japan Storage Battery Co., Ltd. Method for curing photo-curable composition
US4413052A (en) * 1981-02-04 1983-11-01 Ciba-Geigy Corporation Photopolymerization process employing compounds containing acryloyl group and anthryl group
US5512329A (en) * 1982-09-29 1996-04-30 Bsi Corporation Substrate surface preparation
US5741551A (en) * 1982-09-29 1998-04-21 Bsi Corporation Preparation of polymeric surfaces
WO2001097217A3 (en) * 2000-06-16 2002-05-02 Optilink Ab Optical storage using materials comprising chromophore oligomers which can undergo cycloaddition
US7326510B2 (en) 2001-11-01 2008-02-05 Evangelos Gogolides Polycarbocyclic derivatives for modification of resist, optical and etch resistance properties
US20050026068A1 (en) * 2001-11-01 2005-02-03 Evangelos Gogolides Polycarbocyclic derivatives for modification of resist, optical and etch resistance properties
US20040027625A1 (en) * 2002-04-11 2004-02-12 Inphase Technologies Holographic storage media
WO2003088234A1 (en) * 2002-04-11 2003-10-23 Inphase Technologies, Inc. Holographic storage media
US7521154B2 (en) 2002-04-11 2009-04-21 Inphase Technologies, Inc. Holographic storage media
US20090253050A1 (en) * 2002-04-11 2009-10-08 Inphase Technologies, Inc. Holographic storage media
US8062809B2 (en) 2002-04-11 2011-11-22 Inphase Technologies, Inc. Holographic storage media
WO2019002273A1 (en) * 2017-06-26 2019-01-03 Solvay Specialty Polymers Usa, Llc AROMATIC POLYMERS THAT CAN BE OBTAINED BY CYCLOADDITION REACTION

Also Published As

Publication number Publication date
GB1358274A (en) 1974-07-03
DE2212427A1 (de) 1972-09-28
FR2130443A1 (cg-RX-API-DMAC10.html) 1972-11-03
FR2130443B1 (cg-RX-API-DMAC10.html) 1977-04-01
BE780294A (nl) 1972-07-03

Similar Documents

Publication Publication Date Title
US3558309A (en) Photopolymerisation of ethylenically unsaturated organic compounds
Nagata et al. Photoreversible poly (ethylene glycol) s with pendent coumarin group and their hydrogels
US4181807A (en) Polymerizable esters derived from a glycidyl ether of a phenolic unsaturated ketone
US3807999A (en) Photo-cycloaddition polymerization of bis-anthracenes
US3558311A (en) Photographic material comprising light-sensitive polymers and photodegradation process
Höfler et al. UV reactive polymers for refractive index modulation based on the photo-Fries rearrangement
JP5486141B2 (ja) 光開始反応
Egerton et al. Photocycloaddition at excimer sites in a solid polyester of p-phenylenediacrylic acid
US3149975A (en) Photopolymerizable compositions and elements
US3892642A (en) Photo-cycloaddition polymerization of bis-anthracene
Carlsson et al. Photodegradation of aramids. I. Irradiation in the absence of oxygen
De Schryver et al. Photocycloaddition polymerization. I. Preparation and characterization of poly‐N, N′‐polymethylenebisdichloromaleimides
US3721566A (en) Increasing the light sensitivity of polymeric compositions comprising azido groups
Griesser et al. Refractive index modulation in polymers bearing photoreactive phenyl and naphthyl ester units using different UV wavelengths
US3982942A (en) Photopolymerization of ethylenically-unsaturated organic compounds
Bratschkov et al. Synthesis and photochemical transformations of an anthracene containing methacrylic copolymer
US4822682A (en) Oriented polymer materials
Simbürger et al. Photoreactions in polymers containing benzil units: a comparative study under excimer laser and Hg-lamp irradiation
Chae et al. Application of an anthracene containing polymer to a negative type photoresist
Tajima et al. Application of a furan-containing polymer/fullerene system to photolithography
Finter et al. A new class of photopolymers with pendent dimethylmaleimide groups. III. Comparative study of different photopolymers with pendent olefinic structures including dimethylmaleimide groups
US3429795A (en) Photopolymerisation of ethylenically unsaturated organic compounds using a carboxylic dithiocarbamic anhydride as a photoinitiator
US3729405A (en) Photocycloaddition polymerisation of bis-coumarins
US3309297A (en) Polymerization of vinyl esters
US3486903A (en) Photopolymerizable compositions and their use